Epoxy resin compositions containing a partial acid-addition salt of aromatic polyamine and water soluable amine

ABSTRACT

Water-cleanable epoxy resin compositions capable of curing rapidly at ambient temperatures which contain an epoxy resin, a partial acid-addition salt of an aromatic polyamine and a watersoluble, strongly basic amine are described.

AU 116 EX United States Patent 91 Wagner et al.

[73] Assignee: Tile Council of America Inc., New

York, N.Y.

[22] Filed: April 6, 1970 [21] Appl. No.: 26,112

[52] US. Cl ..260/47 EN, 106/39 R, 106/89, 117/161 ZB, 117/169 R, 260/2N, 260/29.I

R, 260/30.2, 260/37 EP, 260/59, 260/830 R,

[51] Int. Cl. ..C08g 30/14 [58] Field 01 Search....260l47 EP, 2 EP, 59,29.2 EP, 260/18 EP [11] 3,718,618 51 Feb. 27, 1973 [56] References CitedUNITED STATES PATENTS 3,277,052 10/ 1966 Thompson et al ..260/472,965,517 12/ 1960 Albrecht et al. .260/29.2 EP 2,681,901 6/1954 Wileset al. 260/47 EP 3,018,258 1/1962 Meier et 260/47 EP 3,347,802 10/1967Ashby et a1. .....260/29.2 EP 3,305,501 2/1967 Primary Examiner-WilliamH. Short Assistant Examiner-T. Pertilla Attorney-Morgan, Finnegan,Durham & Pine [57] ABSTRACT WIWOmpOsitims capable of curing rapidly atam rent te eratures which contain an epoxy resin, a partialacid-addition salt of an aromatic polyamine and a water-soluble,strongly basic amine are described.

15 Claims, No Drawings Spalding ..260/29.2 EP

EPOXY RESIN COMPOSITIONS CONTAINING A PARTIAL ACID-ADDITION SALT OFAROMATIC POLYAMINE AND WATER SOLUABLE AMINE BACKGROUND OF THE INVENTIONThis invention relates to epoxy resins which are hardened by aromaticamines. More particularly, it relates to aromatic amine hardening epoxyresins which may be cured at practical rates under ambient temperatureconditions.

It relates further to novel epoxy resin compositions which may be easilywater cleaned from areas in which they have been installed or applied.

Prior to this invention, the epoxy-aromatic amine systems which wereknown, reacted at a much lower rate in the hardening process as comparedwith that of epoxy-aliphatic amine systems so that utilization underthese conditions was precluded. Since many situations exist where a roomtemperature cure is essential and since epoxy resins harden by reactionwith aromatic amines are known to have superior chemical resistance, theattractiveness of compositions as disclosed and claimed herein becomesapparent. In addition, no epoxy compositions hardened by aromatic amineswere known prior to this time which were capable of being water cleanedresulting in the easy removal of the fluid mixtures of epoxy resin andhardener from areas and tools immediately after the epoxy resincomposition had been installed or applied. The subject compositionspermit the use of water rather than noxious or inflammable organicsolvents to facilitate this cleaning operation.

The compositions of the present invention, therefore, provide rapid roomtemperature hardening and the ability to be water cleaned whilesimultaneously retaining the inherent chemical resistance of epoxyresins cured by aromatic amines.

SUMMARY OF THE INVENTION Accordingly, this invention discloses andclaims a water-cleanable epoxy resin composition which can be curedrapidly at ambient temperatures which comprises an epoxy resin, apartial acid-addition salt of an aromatic polyamine and a water-soluble,strongly basic amine.

Of particular importance are those compositions in which the epoxy resinis a bisphenol A- epichlorohydrin, novolak or polyglycol-type resin.Particularly preferred aromatic polyamines which are used in the hereindisclosed compositions are benzidine, 4,4-methylenedianiline,4,4'-ethylenedianiline, 4,4- methylenedi-( naphthyl-amine), mandp-aminoaniline and mand p-phenylenediamine. The aromatic polyamine is inthe form of a partial acid-addition salt wherein said acid is inorganicor organic and is present in an amount sufficient to neutralize from 30per cent to about 80 per cent of the amino nitrogens. Still anotherpreferred embodiment of the present invention is the use of highlybasic, water-soluble amines such as triethylamine and triethanolaminewhich possess ionization constants greater than said aromatic polyamine.

It has also been found that the cleaning step is facilitated by the useof surface active agents. Particularly effective are sodium alkylsulfonate surfactants.

DETAILED DESCRIPTION OF THE INVENTION The fundamental components whichmake up the presently disclosed compositions having the ability to curerapidly at room temperature are: (1) an epoxyv resin; (2) a partialacid-addition salt of an aromatic polyamine; and (3) a water-soluble,strongly basic amine.

On a per cent by weight basis, the following amounts of each componentis preferred:

epoxy resin 5 to 20% by weight acid-addition salt of polyamine 2 to 8%by weight basic amine 0.5 to 2% by weight The above percentages arebased on the total weight of the composition. It will be obvious that inorder to total percent, materials such as fillers, resins, pigments,coloring materials and adhesives, etc., will necessarily comprise thebalance.

It is also beneficial to include a surfactant to the above composition.Particularly preferred is a sodium alkyl sulfonate; however, many otherswill be equally applicable such as sodium alkylnaphthalene sulfonates,sodium alkylaryl sulfonates and chlorosulfonated paraffinichydrocarbons. Although the surfactant can comprise from about I to about5 percent by weight of the total composition, most preferred is a 2 to 3percent by weight concentration.

Most preferred is a composition having about 10 percent by weight ofepoxy resin, about 5 percent by weight of acid-addition salt of aromaticpolyamine, about l percent by weight of water-soluble, basic amine andabout 2.5 percent by weight of surfactant.

With regard to the epoxy resin component, it is found that certain typesare most preferred for utilization in the compositions of thisinvention. They include bisphenol A-epichlorohydrin resins which areprepared by reaction of epichlorohydrin with bisphenol- A in thepresence of catalyst. They have the structural formula:

(I311; O in 5 where n has a value averaging from 0 to 18.

Another highly desirable resin is the novolak type resin having thestructural formula:

H... was... bmvwhere n has a value averaging from 0.2 to

Still another highly desirable resin for purposes of this invention isthe polyglycol type having the formula:

where n has a value averaging from 3 to 6; R and R are each hydrogen,methyl or ethyl.

Although the n values may vary as indicated above for each resin, it ismost advantageous to have the epoxy resin of such molecular weight thatit is in liquid form at ambient temperatures. It has also beendiscovered that the most advantageous epoxy resins, insofar as thehardening step is concerned, are those in which the epoxy group carbonsare acyclic rather than cyclic.

Epoxy resins can be cured by a variety of cross-linking agents known ashardeners. When nearly all the reactive sites in the resin have beenreacted, the system becomes a tough, infusible material and isconsidered cured. The cross-linking agents (hardeners) are mixed into,and react with, the epoxy resin. These hardeners contain reactive groupswhich react with the epoxy groups and become integral parts of themolecular stiucture.

The hardeners or cross-linking agents which provide the highlyadvantageous compositions of this invention comprise two types: apartial acid-addition salt of an aromatic polyamine and a strongly basicamine. The aromatic polyamine is defined for purposes of this inventionto be any dior poly-functional primary or secondary amine or mixturesthereof wherein the amine nitrogens are bonded directly to the aromaticnucleus. Illustrative examples include benzidine, 4,4-methylenedianiline, 4,4'-ethylenedianiline, 4,4-methylenedi(naphthyl-amine), mand p-aminoaniline and mandp-phenylenediamine.

The aromatic polyamine is used herein in the form of a partialacid-addition salt. The salt is prepared by reacting the aromatic aminewith an acid, inorganic or organic, whereby the amount of acid added issuch that from about 30 percent to about 80 percent of the aminonitrogens are neutralized stoichiometrically.

Most preferred is the partial salt wherein about 50 percent of the aminonitrogens are neutralized.

The acids used to prepare the subject salts may be inorganic such ashydrochloric, hydrobromic, hydroiodic, nitric, phosphoric, sulfuric,sulfamic, sulfurous, etc. or organic such as acetic, chloroacetic,ptoluene sulfonic, lactic, citric, tartaric, oxalic, succinic, maleic,gluconic, etc.

The second type of hardener used in preparing the herein disclosedcompositions is defined as a strongly basic amine. By the term "stronglybasic amine" is contemplated any amine which is water-soluble and has anionization constant greater than the aromatic polyamine used in makingthe aforesaid partial acid-addition salt. Illustrative of such stronglybasic amines" are primary, secondary and tertiary alkylamines whereinsaid alkyl group contains from one to 12 carbon atoms, alkylene diamineswherein said alkylene group contains from two to six carbon atoms andmon-, diand tri-hydroxyamines such as ethanolamine, diethanolamine andtriethanolamine.

If desired, the epoxy resins can be compounded with other resins, suchas polystyrene resins, polyester resins, and so forth, to increase theflexibility of the hardened composition.

Pigments and fillers of various types may also be incorporated into theadhesive compositions. As examples of such fillers may be mentionedblanc fixe, sand, talc, pyrophyllite, various clays, diatomaceous earth,and other like materials. The fillers are preferably in a fine state ofsubdivision, and have high surface areas.

Coloring materials may be added to the adhesive composition if desired.The coloring materials include organic and inorganic coloring materials.As examples may be mentioned titanium dioxide, carbon black, cadmiumred, Blue Lake (13 percent Ponsal Blue, 10 percent aluminum hydrate and77 per cent blanc fixe)- Krebs BP-l79-D, Blue Lake Krebs BP-258-D,Lithol Tower, Chrome Yellow, Iron Blue, Milori Blue, Monastral Green,Maron Toner, chrome green, chrome orange, iron oxide reds, aluminumpowder, and flating agents like diatomaceous silica and silica aerogel.The coloring materials should be selected, however, so as to benon-reactive with the epoxy resins and other ingredients at atmospherictemperature, as otherwise this -might cause poor storage stability andalso affect the retention of adhesiveness.

The adhesive compositions of the present invention may also haveincorporated therein, if desired, a lubricant, such as silicone oils,silicone jelly, petroleum jellies, and so forth. As an example of thesilicone oil may be mentioned organo-siloxane liquid supplied by GeneralElectric Company as Silicone Liquid No. 81069. Any of the commerciallyavailable silicone jellies which are sold under a wide variety oftrademarks and trade names may be used.

EXAMPLE I 4,4'-methylenedianiline (5.0 g.) is added to a solutioncontaining 2.5 g. of concentrated HCl (37 percent) in 100 g. of water.The resulting suspension is then heated to about C. with agitation. Thereaction is almost instantaneous as evidenced by the formation of asolution. The solution corresponds to a 50% neutralized amine product.Upon partial evaporation of solvent and cooling, the precipitatedpartial acid-addition salt of amine is filtered and dried.

The above amine salt (10.0 g.) is then mixed with 7.5 g. oftriethanolamine and 34 g. of a liquid epichlorohydrin-2,2-bis(p-hydroxyphenyl) propane type epoxy resin having an epoxide equivalentweight of about 180. A portion of this composition is set aside forhardening under ambient conditions. Hardening occurred within 24 hoursafter mixing. A second portion is spread over the face of a vitreousceramic tile, of the type frequently used where a flooring exhibitingsubstantial chemical resistance is required. No difficulty was found incleaning the liquid composition from the tile face with a water-wettedsponge.

EXAMPLE II The procedure of Example I is repeated wherein benzidene instoichiometric equivalent amounts, is used in lieu of4,4'-methylenedianiline with good results.

EXAMPLE Ill The procedure of Example I is repeated whereinmphenylenediamine, in stoichiometric equivalent amounts, is used in lieuof 4,4'-methylenedianiline with good results.

EXAMPLE IV The procedure of Example I is repeated whereinpphenylenediamine, in stoichiometric equivalent amounts, is used in lieuof 4,4-methylenedianiline with good results.

EXAMPLE V The procedure of Example I is repeated wherein the followingaromatic polyamines, in stoichiometric equivalent amounts, are used inplace of 4,4- methylenediamine with good results: 4,4'-ethylenedianiline4,4'-methylenedi(a-naphthylamine) 4,4'-methylenedi(B-naphthylamine)m-aminoaniline p-aminoaniline EXAMPLE VI The procedure of Example I isrepeated wherein triethylamine, in stoichiometric equivalent amounts, is

used in place of triethanolamine with correspondingly good results.

EXAMPLE VII The procedure of Example I is repeated wherein the followingwater-soluble, strongly basic amines, in' stoichiometric equivalentamounts, are used in lieu of triethanolamine with correspondingly goodresults:

The procedure of Example I is repeated wherein a typical novolak resin,in equivalent amounts, is used in place of the bisphenol Aepichlorohydrin resin to provide the corresponding product in goodyields.

Similarly, a typical polyglycol type resin, in equivalent amounts, isused in lieu of the bisphenol A epichlorohydrin resin to provide thecorresponding product in good yields.

EXAMPLE [X The procedure of Example I is repeated wherein the followingacids, in stoichiometric equivalent amounts,

are used in place of HC] with correspondingly good results:

phosphoric acid acetic acid sulfuric acid chloroacetic acid sulfamicacid p-toluenesulfonic acid EXAMPLE X The procedure of Example I isrepeated wherein 4 g. of surfactant, Alkanol 189-5 (Alkanol 189-S is atrademark of du Pont) a sodium alkyl sulfonate having a molecular weightof about 345 is added. The cleaning step is further facilitated by itsinclusion in the composition.

EXAMPLE XI Other ingredients may be advantageously incorporated into theherein disclosed compositions. The following composition is a typicalcomposition which contains many of these ingredients:

Component Parts by Weight Epoxy resin EPON 828" iii Phenyl glycidylether (Fluidity improver) 3 Petroleum jelly (lubricant) 1.5 Carbon black(coloring agent) 0.1 Alkanol l89-S (surfactant) 4.0 Polystyrene resin(extender) 10.0 50% neutralized 4,4

-dimethylenedianiline 10.0 Sand (filler) l30.0 Triethanolamine-silicaaerogel (1:4) l0.0

"An epichlorohydrin-bisphenol type epoxy resin sold under the trademarkEpon Resin 828" by Shell Chemical Corporation.

What is claimed is:

l. A water-cleanable epoxy resin composition which cures rapidly atambient temperatures comprising an epoxy resin selected from the groupconsisting of bisphenol A epichlorohydrin resins, polyglycidyl ethers ofnovalak resins and diglycidylethers of 'polyglycol resins, a partialacid-addition salt of an aromatic polyamine derived from an acid presentin an amount sufficient to neutralize from about 30 percent to aboutpercent of the amine nitrogens, said salt comprising from about 2percent to about 8 percent by weight of the total composition, and awater-soluble, strongly basic amine having an ionization constantgreater than said aromatic polyamine selected from the group consistingof alkylamines, alkylenediamines and mono-, diand trihydroxyalkylamines,said strongly basic amine comprising from about 0.5 to about 2.0 percentby weight of the total composition.

2. The composition of claim 1 wherein a surface active agent isincluded.

3. The composition of claim 2 wherein said surface active agent is asodium alkyl sulfonate.

4. The composition of claim 1 wherein said epoxy resin comprises fromabout 5 percent to about 20 percent by weight of the total composition.

5. The composition of claim 1 wherein said aromatic polyamine isselected from the group consisting of polyfunctional primary andsecondary amines and mix- 11. The composition of claim 1 wherein saidacid is an inorganic acid selected from the group consisting ofphosphoric acid, sulfuric acid, sulfamic acid and hydrochloric acid.

12. The composition of claim 11 wherein said acid is hydrochloric acid.

13. The composition of claim 1 wherein said acid is an organic acidselected from the group consisting of acetic acid, chloroacetic acid andp-toluene sulfonic acid.

14. The composition of claim 1 wherein said strongly basic amine istriethylamine.

15. The composition of claim 1 wherein said strongly basic amine istriethanolamine.

2. The composition of claim 1 wherein a surface active agent isincluded.
 3. The composition of claim 2 wherein said surface activeagent is a sodium alkyl sulfonate.
 4. The composition of claim 1 whereinsaid epoxy resin comprises from about 5 percent to about 20 percent byweight of the total composition.
 5. The composition of claim 1 whereinsaid aromatic polyamine is selected from the group consisting ofpolyfunctional primary and secondary amines and mixtures thereof whereinthe amine nitrogens are bonded directly to the aromatic nucleus.
 6. Thecomposition of claim 5 wherein said aromatic polyamine is selected fromthe group consisting of benzidine, 4,4''-methylenedianiline,4,4''-ethylenedianiline, 4,4''-methylenedi-(naphthyl-amine), m- andp-aminoaniline and m- and p-phenylenediamine.
 7. The composition ofclaim 6 wherein said polyamine is benzidine.
 8. The composition of claim6 wherein said polyamine is 4,4''-methylenedianiline.
 9. The compositionof claim 6 wherein said polyamine is m-phenylenediamine.
 10. Thecomposition of claim 6 wherein said polyamine is p-phenylenediamine. 11.The composition of claim 1 wherein said acid is an inorganic acidselected from the group consisting of phosphoric acid, sulfuric acid,sulfamic acid and hydrochloric acid.
 12. The composition of claim 11wherein said acid is hydrochloric acid.
 13. The composition of claim 1wherein said acid is an organic acid selected from the group consistingof acetic acid, chloroacetic acid and p-toluene sulfonic acid.
 14. Thecomposition of claim 1 wherein said strongly basic amine istriethylamine.
 15. The composition of claim 1 wherein said stronglybasic amine is triethanolamine.